CN111164804B - Silicon-based negative electrode material, preparation method thereof and lithium ion battery - Google Patents

Silicon-based negative electrode material, preparation method thereof and lithium ion battery Download PDF

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CN111164804B
CN111164804B CN201980003461.5A CN201980003461A CN111164804B CN 111164804 B CN111164804 B CN 111164804B CN 201980003461 A CN201980003461 A CN 201980003461A CN 111164804 B CN111164804 B CN 111164804B
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silicon
coating layer
carbon coating
silicon substrate
substrate material
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CN111164804A (en
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刘冬冬
马飞
吴玉虎
魏良勤
吴志红
丁晓阳
李凤凤
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Shanghai Shanshan Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The application provides a silicon-based negative electrode material, a preparation method thereof and a lithium ion battery. The silicon-based negative electrode material comprises: a silicon base material; an amorphous carbon coating layer; and the graphitized carbon coating layer, wherein the amorphous carbon coating layer or the graphitized carbon coating layer is directly coated on the surface of the silicon substrate material. The silicon-based negative electrode material and the preparation method thereof improve the cycle capacity of the silicon-based negative electrode material, have simple process and are suitable for large-scale industrial production.

Description

Silicon-based negative electrode material, preparation method thereof and lithium ion battery
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a silicon-based negative electrode material, a preparation method thereof and a prepared lithium ion battery.
Background
In recent years, higher demands have been made on energy density of lithium ion batteries, and thus, higher capacity negative electrode materials have been required. Currently, silicon-oxygen cathodes have begun to be applied to power batteries, and are in a rapidly growing trend.
Because of the poor conductivity of silica materials, it is necessary to coat a layer of conductive material on the surface of the particles, which is most widely coated with carbon. The carbon coating is not only beneficial to improving the conductivity, but also has a certain constraint effect on the volume expansion of the silicon-oxygen particles after lithium intercalation.
Currently, there are two main methods for carbon coating of silica particles: liquid phase coating and gas phase coating. Because silica particles are small and the surface valence bond polarity is large, the liquid phase coating method has large problems in the aspects of particle dispersion and coating uniformity, and the mass production scale is difficult to achieve. The Chemical Vapor Deposition (CVD) method can conveniently prepare composite particles with uniform coating and low particle adhesion, so the mainstream technology at present is the CVD method. The method comprises the following steps of putting raw materials into a rotary furnace, a rotary furnace and other equipment, setting the temperature to be 700-1050 ℃, directly introducing carbon-containing gas or steam, and forming a continuous carbon layer on the surface layer of silica particles in the same reaction cavity through reactions such as pyrolysis, polycondensation and the like.
Because of disproportionation reaction of SiO at high temperature, the temperature of the conventional CVD coating method is generally lower than 1000 ℃, only one layer of amorphous carbon can be deposited on the surface of the particles, the carbon layer is loose, and the binding capacity of the coating layer on the particles is relatively small. When the silicon-oxygen particles are subjected to lithium intercalation, the volume change is huge, the coating layer is extremely easy to crack, a new SEI film is formed, and the SEI film is gradually thickened along with circulation, so that the results of serious gas generation, poor circulation and the like of the lithium battery are caused. Due to the loose structure of the coating layer, the negative active material is easy to deactivate after lithium removal, namely, an effective conductive network cannot be formed due to poor electrical contact to lose electrochemical activity, so that the capacity of the lithium battery is attenuated too fast. Although the coating amount is increased, the cracking of the coating layer caused by the change of the volume of lithium intercalated and deintercalated can be relieved, the excessively high content of the coating layer also causes lower capacity and first coulombic efficiency, and further causes the reduction of the energy density of the lithium ion battery prepared by the material.
Therefore, it is desirable to provide a new silicon-based anode material and a method for manufacturing the same.
Disclosure of Invention
The technical problem to be solved by the technical scheme is to provide a novel silicon-based negative electrode material and a manufacturing method thereof and provide a lithium ion battery comprising the silicon-based negative electrode material aiming at the defects that an amorphous carbon coating layer structure contained in the silicon-based negative electrode material in the prior art is easy to crack and the performance of the battery is influenced.
One aspect of the present application provides a method for preparing a silicon-based anode material, including: in a non-oxidizing atmosphere, making a carbon source substance pass through a pre-decomposition area to form decomposition products, wherein the carbon source substance comprises more than one of a gas carbon source substance, a vaporized carbon source substance or an atomized carbon source substance; and regulating and controlling the flow velocity V of the decomposition product entering the reaction cavity of the deposition coating areaGAnd the molar flow rate of the decomposition product and the mass ratio Mc/M of the silicon substrate material are used for leading the silicon substrate material and the decomposition product to generate deposition coating reaction in a deposition coating area, forming an amorphous carbon coating layer and a graphitized carbon coating layer on the surface of the silicon substrate material, and directly coating the amorphous carbon coating layer or the graphitized carbon coating layer on the surface of the silicon substrate material, wherein V is more than or equal to 0.01 and less than or equal to VG≤100，0.001≤Mc/M≤1，VGThe unit is M/min, MCThe unit is mol/min, and M is the mass of the silicon substrate material in kg by carbon atoms.
In some embodiments of the present application, in a first condition: v is more than or equal to 10GWhen Mc/M is less than or equal to 100 and 0.001 and less than 0.1, a graphitized carbon coating layer is formed on the surface of the silicon substrate material; in a second condition: v is more than or equal to 0.01GWhen Mc/M is more than 0.2 and less than or equal to 1, an amorphous carbon coating layer is formed on the surface of the silicon substrate material.
In some embodiments of the present application, adjusting the VGAnd the value of Mc/M is alternately switched between a first condition and a second condition, and an amorphous carbon coating layer and a graphitized carbon coating layer which are alternately coated are formed on the surface of the silicon substrate material.
In some embodiments of the present application, the gaseous carbon source material comprises methane, ethane, ethylene, acetylene, propane, propylene, the vaporized carbon source material comprises n-hexane, ethanol, benzene, and the atomized carbon source material comprises polyethylene, polypropylene.
In the present applicationIn some embodiments, during the deposition coating reaction, a N-containing substance may be introduced, where the N-containing substance includes NH3One or more of acetonitrile, aniline or butylamine.
In some embodiments herein, the non-oxidizing atmosphere refers to a reaction environment comprising any one or more of hydrogen, nitrogen, or an inert gas.
In some embodiments of the present application, the pre-decomposed carbon source material is at a temperature in a range of 500 ℃ to 1500 ℃.
In some embodiments of the present application, the temperature at which the deposition coating reaction occurs is 500 ℃ to 1100 ℃.
In some embodiments of the present application, the pre-decomposed carbon source material has a temperature ranging from 700 ℃ to 1300 ℃, and the deposition coating reaction occurs at a temperature ranging from 650 ℃ to 1000 ℃.
In some embodiments of the present application, the silicon substrate material comprises one or more of metallurgical silicon, silicon oxide SiOx (0. ltoreq. x. ltoreq. 1.5) and porous silicon, and the median particle size of the silicon substrate material is in a range of 1 μm-20 μm.
In some embodiments of the present application, the silicon substrate material further comprises a compound of the formula MSiOy, wherein y is greater than 0.85 and less than or equal to 3.5; m is any one or more of Li, Na, Mg, Al, Fe and Ca.
The present application also provides a silicon-based anode material, including: a silicon base material; an amorphous carbon coating layer; and the graphitized carbon coating layer, wherein the amorphous carbon coating layer or the graphitized carbon coating layer is directly coated on the surface of the silicon substrate material.
In some embodiments of the present application, the amorphous carbon coating has a raman spectrum Id/Ig > 0.7 and the graphitized carbon coating has a raman spectrum Id/Ig < 0.5.
In some embodiments of the present application, the heating is carried out in an air atmosphere, and the oxidation initiation temperature of the amorphous carbon coating is 400 ℃ or less and the oxidation initiation temperature of the graphitized carbon coating is 450 ℃ or more.
In some embodiments of the present application, the amorphous carbon coating layer is doped with nitrogen atoms, and the graphitized carbon coating layer is doped with nitrogen atoms.
In some embodiments of the present application, the surface of the silicon substrate material includes more than one amorphous carbon coating layer and more than one graphitized carbon coating layer, and the more than one amorphous carbon coating layers and the more than one graphitized carbon coating layers are alternately arranged.
In some embodiments of the present application, each of the amorphous carbon coating layers has a thickness ranging from 1nm to 20nm, and each of the graphitized carbon coating layers has a thickness ranging from 1nm to 20 nm.
In some embodiments of the present application, the sum of the thicknesses of the amorphous carbon coating layer and the graphitized carbon coating layer on the surface of the silicon substrate material is 1nm to 1000 nm.
In some embodiments of the present application, the amorphous carbon coating layer is present in the silicon-based negative electrode material in an amount of 1 to 10% by mass, and the graphitized carbon coating layer is present in the silicon-based negative electrode material in an amount of 1 to 10% by mass.
In some embodiments of the present application, the silicon substrate material comprises one or more of metallurgical silicon, silicon oxide SiOx (0. ltoreq. x. ltoreq. 1.5) and porous silicon, and the median particle size of the silicon substrate material is in a range of 1 μm-20 μm.
In some embodiments of the present application, the silicon substrate material further comprises a compound of the formula MSiOy, wherein y is greater than 0.85 and less than or equal to 3.5; m is any one or more of Li, Na, Mg, Al, Fe and Ca.
The application also provides a lithium ion battery, and the negative electrode of the lithium ion battery comprises the silicon-based negative electrode material.
The silicon-based negative electrode material provided by the embodiment of the application has the advantages that the amorphous carbon coating layer and the graphitized carbon coating layer are formed on the surface of the silicon substrate material, so that the charge-discharge cycle capacity of the silicon-based negative electrode material is improved, and the service life of a secondary battery is further prolonged.
In addition, the embodiment of the application also provides a manufacturing method of the silicon-based negative electrode material, and the whole preparation process of the method is simple to operate and is very suitable for industrial production.
Additional features of the present application will be set forth in part in the description which follows. The descriptions of the figures and examples below will become apparent to those of ordinary skill in the art from this disclosure. The inventive aspects of the present application can be fully explained by the practice or use of the methods, instrumentalities and combinations set forth in the detailed examples discussed below.
Drawings
The following drawings describe in detail exemplary embodiments disclosed in the present application. Wherein like reference numerals represent similar structures throughout the several views of the drawings. Those of ordinary skill in the art will understand that the present embodiments are non-limiting, exemplary embodiments and that the accompanying drawings are for illustrative and descriptive purposes only and are not intended to limit the scope of the present disclosure, as other embodiments may equally fulfill the inventive intent of the present application. It should be understood that the drawings are not to scale. Wherein:
fig. 1 is an SEM image of a silicon-based negative electrode material provided in an embodiment of the present application;
fig. 2 is a raman spectrum of an amorphous carbon coating layer and a graphitized carbon coating layer in a silicon-based negative electrode material provided in an embodiment of the present application.
Detailed Description
The following description is presented to enable any person skilled in the art to make and use the present disclosure, and is provided in the context of a particular application and its requirements. Various local modifications to the disclosed embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be applied to other embodiments and applications without departing from the spirit and scope of the present disclosure. Thus, the present disclosure is not to be limited to the embodiments shown, but is to be accorded the widest scope consistent with the claims.
The technical solution of the present invention will be described in detail below with reference to the embodiments and the accompanying drawings.
One aspect of the present application provides a silicon-based negative electrode material that is used in lithium ion batteries. The silicon-based negative electrode material comprises: a silicon base material; an amorphous carbon coating layer; and the graphitized carbon coating layer, wherein the amorphous carbon coating layer or the graphitized carbon coating layer is directly coated on the surface of the silicon substrate material.
That is, an amorphous carbon coating layer and a graphitized carbon coating layer are formed on the surface of the silicon substrate material. In some embodiments of the present application, the amorphous carbon coating layer is directly coated on the surface of the silicon substrate material, and the graphitized carbon coating layer is coated on the surface of the amorphous carbon coating layer. In other embodiments of the present application, the graphitized carbon coating layer is directly coated on the surface of the silicon substrate material, and the amorphous carbon coating layer is coated on the surface of the graphitized carbon coating layer. The coating can be partially or completely coated, and the coating degree of the coating is different according to different manufacturing processes of the silicon-based negative electrode material.
For example, the total coating thickness of the amorphous carbon coating layer and the graphitized carbon coating layer on the surface of the silicon substrate material is 500nm, wherein the amorphous carbon coating layer with the total thickness of 400nm is coated on the surface of the silicon substrate material (the amorphous carbon coating layer with the total thickness of 400nm may include a plurality of single amorphous carbon coating layers with the single thickness of 1nm to 20 nm), and the graphitized carbon coating layer with the total thickness of 100nm is coated on the surface of the amorphous carbon coating layer (the graphitized carbon coating layer with the total thickness of 100nm may include a plurality of single graphitized carbon coating layers with the single thickness of 1nm to 20 nm), and the coating degree of the amorphous carbon coating layer or the graphitized carbon coating layer is relatively high and close to full coating. In the embodiments of the present application, the amorphous carbon coating layer or the graphitized carbon coating layer may be considered to form a full coating structure when the thickness thereof reaches about 5 nm.
For another example, the total coating thickness of the amorphous carbon coating layer and the graphitized carbon coating layer on the surface of the silicon substrate material is 30nm, wherein the graphitized carbon coating layer with the thickness of 5nm, the amorphous carbon coating layer with the thickness of 3nm, the graphitized carbon coating layer with the thickness of 4nm, the amorphous carbon coating layer with the thickness of 2nm, the graphitized carbon coating layer with the thickness of 10nm and the amorphous carbon coating layer with the thickness of 6nm are sequentially coated on the surface of the silicon substrate material.
In the above embodiment, the surface of the silicon substrate material includes more than one amorphous carbon coating layer and more than one graphitized carbon coating layer, and the more than one amorphous carbon coating layers and the more than one graphitized carbon coating layers are alternately arranged. In the structure in which the amorphous carbon coating layers and the graphitized carbon coating layers are alternately arranged, the amorphous carbon coating layers or the graphitized carbon coating layers can be directly coated on the surface of the silicon substrate material.
The amorphous carbon coating layer is a loose amorphous carbon structure and plays a role in buffering lithium insertion expansion of the silicon substrate material, the graphitized carbon coating layer is a high-graphitization-degree crystal form carbon structure and plays a certain role in restricting lithium insertion expansion of the silicon substrate material, and cracking of the coating layer and inactivation of active substances in the lithium insertion and removal process of the silicon substrate material are prevented, so that the amorphous carbon structure and the graphitized carbon coating structure which are alternately arranged can better adjust the charge and discharge performance of the silicon substrate negative electrode material, and the cycle life of the battery is prolonged.
In some embodiments of the present application, each of the amorphous carbon coating layers has a thickness ranging from 1nm to 20nm, and each of the graphitized carbon coating layers has a thickness ranging from 1nm to 20 nm. The sum of the thicknesses of the amorphous carbon coating layer and the graphitized carbon coating layer on the surface of the silicon substrate material is 2 nm-1000 nm. For example, the sum of the thicknesses of the amorphous carbon coating layer and the graphitized carbon coating layer on the surface of the silicon substrate material is 300nm, and the surface of the silicon substrate material comprises amorphous carbon coating layers with the thickness of 10nm and graphitized carbon coating layers with the thickness of 10nm which are alternately arranged for 15 times.
In some embodiments of the present application, the amorphous carbon coating layer is present in the silicon-based negative electrode material in an amount of 1 to 10% by mass, and the graphitized carbon coating layer is present in the silicon-based negative electrode material in an amount of 1 to 10% by mass. The amorphous carbon coating layer and the graphitized carbon coating layer occupyThe mass percentage total amount of the silicon-based negative electrode material is 2-20%. When the outermost layer of the silicon-based negative electrode material is an amorphous carbon coating layer, the specific surface area of the silicon-based negative electrode material is generally higher (1-20 m)2(g), when the outermost graphitized carbon coating layer of the silicon-based negative electrode material is arranged, the specific surface area of the silicon-based negative electrode material is generally lower (0.1-15 m)2/g)。
In some embodiments of the present application, the amorphous carbon coating layer may be present in the silicon-based negative electrode material in an amount of 5%, 3%, or 8% by mass, and the graphitized carbon coating layer may be present in the silicon-based negative electrode material in an amount of 4%, 6%, or 9%, or 5%, or 3%, or 8% by mass. That is, in the silicon-based negative electrode material, the amorphous carbon coating layer and the graphitized carbon coating layer may be the same or different in mass percentage content.
In the examples of the present application, the amorphous carbon coating layer has a raman spectrum Id/Ig > 0.7 and the graphitized carbon coating layer has a raman spectrum Id/Ig < 0.5 as determined by raman spectroscopy. In a heating test in an air atmosphere, the oxidation initial temperature of the amorphous carbon coating layer is less than or equal to 400 ℃, and the oxidation initial temperature of the graphitized carbon coating layer is more than or equal to 450 ℃. Since the structure of the silicon-based negative electrode material plays a decisive role in the oxidation initiation temperature, the oxidation initiation temperatures of the amorphous carbon coating layer and the graphitized carbon coating layer represent the coating layer properties of the silicon-based negative electrode material.
The intensity of a D peak in a Raman spectrum represents the disorder degree of the carbon layer, and the intensity of a G peak represents the ordering degree of the material, namely Id/Ig can effectively represent the graphitization degree of the carbon layer. In the oxidizing atmosphere, the oxidation initiation temperature point of the amorphous carbon is lower, and the oxidation initiation temperature point of the graphitized carbon is higher.
In some embodiments of the present application, the amorphous carbon coating layer may further be doped with nitrogen atoms. The graphitized carbon coating layer may be doped with nitrogen atoms. The nitrogen atom may be derived from a N-containing species such as NH3One or more of acetonitrile, aniline or butylamine. In the amorphous carbon coating layerAnd the graphitized carbon coating layer is added with nitrogen atoms, so that the charge-discharge capacity of the silicon-based negative electrode material can be further improved, and the conductivity of the material can be further improved after nitrogen doping, so that the internal resistance of the battery is reduced, and the large-current charge-discharge capacity of the battery is further ensured.
In some embodiments of the application, the silicon substrate material comprises one or more of metallurgical silicon, silicon oxide SiOx (0 ≦ x ≦ 1.5) and porous silicon, and the median particle size of the silicon substrate material ranges from 1 μm to 20 μm. In some embodiments of the present application, the silicon substrate material further comprises a compound of the formula MSiOy, wherein y is greater than 0.85 and less than or equal to 3.5; m is any one or more of Li, Na, Mg, Al, Fe and Ca.
The silicon-based negative electrode material provided by the embodiment of the application has the advantages that the amorphous carbon coating layer and the graphitized carbon coating layer are formed on the surface of the silicon substrate material, so that the charge-discharge cycle capacity of the silicon-based negative electrode material is improved, and the service life of a secondary battery is further prolonged.
In addition, the embodiment of the application also provides a manufacturing method of the silicon-based negative electrode material, and the whole preparation process of the method is simple to operate and is very suitable for industrial production.
The embodiment of the application provides a preparation method of a silicon-based negative electrode material, which comprises the following steps: in a non-oxidizing atmosphere, making a carbon source substance pass through a pre-decomposition area to form decomposition products, wherein the carbon source substance comprises more than one of a gas carbon source substance, a vaporized carbon source substance or an atomized carbon source substance; regulating and controlling the flow velocity V of the decomposition product entering the reaction cavity of the deposition coating areaGAnd the molar flow rate of the decomposition product and the mass ratio Mc/M of the substrate material are used for leading the silicon substrate material and the decomposition product to generate deposition coating reaction in a deposition coating area, forming an amorphous carbon coating layer and a graphitized carbon coating layer on the surface of the silicon substrate material, and directly coating the amorphous carbon coating layer or the graphitized carbon coating layer on the surface of the silicon substrate material, wherein V is more than or equal to 0.01 and less than or equal to VG≤100，0.001≤Mc/M≤1，VGThe unit is M/min, MCThe unit is mol/min, calculated by carbon atoms, M is the mass of the silicon substrate materialBit kg.
The silicon-based negative electrode material can be prepared by using coating equipment such as a rotary furnace, a rotary furnace and the like so as to achieve the purpose of uniform coating. The cladding apparatus may be configured to include a pre-decomposition zone and a deposition cladding zone, both of which comprise a reaction chamber. Wherein the pre-decomposition area is used for pre-decomposing the carbon source substances. For example, the carbon source substance is introduced into a pre-decomposition area of the coating device, and the carbon source substance is pyrolyzed, cracked, polycondensed and the like in a non-oxidizing atmosphere to become a gaseous substance. Wherein low molecular weight substances in the carbon source substances are subjected to pyrolysis, polycondensation, addition and other reactions to form medium and large molecular weight substances; the high molecular weight material is cracked into medium and small molecular weight material, and the pyrolysis, polycondensation, addition and other reactions are also accompanied.
The gas providing the non-oxidizing atmosphere includes, for example, any one or more of hydrogen, nitrogen, or an inert gas for serving as a shielding gas, a carrier gas, and a diluting gas for the pre-decomposition zone reaction.
The gas carbon source substances comprise hydrocarbons and aldehydes, the hydrocarbons and the aldehydes are gaseous at room temperature, the gas carbon source substances comprise methane, ethane, ethylene, acetylene, propane and propylene,
the vaporized carbon source substance is a carbon-containing substance which is liquid at room temperature and is gaseous above the room temperature but below the temperature of the pre-decomposition area, and comprises n-hexane, ethanol and benzene.
The atomized carbon source material is a material which is difficult to evaporate by heating, and can be made into small liquid drops through an atomization device, for example, a material which is liquid when the temperature is lower than the temperature of the pre-decomposition area. The atomized carbon source material comprises polyethylene and polypropylene.
In some embodiments of the present application, the flow velocity V of the decomposition products into the reaction chamber of the deposition coating zone is controlledGAnd the value of the ratio of the molar flow rate of the decomposition products to the mass of the substrate material Mc/M is used for leading the silicon substrate material and the decomposition products to carry out deposition coating reaction in a deposition coating area so as to form amorphous carbon coating on the surface of the silicon substrate materialA layer and a graphitized carbon coating layer. Wherein V is more than or equal to 0.01GNot more than 100, not less than 0.001 and not more than 1 Mc/M, the unit of VG is M/min, the unit of MC is mol/min, and the unit of M is the mass of the silicon substrate material in kg by carbon atoms.
In a first condition: v is more than or equal to 10GWhen Mc/M is less than or equal to 100 and 0.001 and less than 0.1, a graphitized carbon coating layer is formed on the surface of the silicon substrate material; in a second condition: v is more than or equal to 0.01GWhen Mc/M is more than 0.2 and less than or equal to 1, an amorphous carbon coating layer is formed on the surface of the silicon substrate material. That is to say, the process for manufacturing the silicon-based negative electrode material according to the embodiment of the present application can adjust the thickness of the amorphous carbon coating layer and the graphitized carbon coating layer formed and the condition of alternate coating by only adjusting the flow rate and mass of the reactants and the reaction time. After the thickness of one coating layer reaches a set value, the flow and the mass of reactants are quickly adjusted, and then the other coating layer can be switched. Of course, in an actual process, the flow rate and the mass adjustment speed of the reactants are set to be slow, and there may be a composite coating layer including two crystal forms of an amorphous carbon coating layer and a graphitized carbon coating layer.
That is, by regulating VG(m/min)、Mc/M(MCUnit mol/min, in terms of carbon atoms, M is the mass of the silicon substrate material, unit kg) can control the crystal structure of the coating layer, thereby obtaining an amorphous carbon coating layer and a graphitized carbon coating layer. Meanwhile, the mass percentage content of the carbon coating layer is adjusted by combining the reaction time.
The running speed of the silicon substrate material and the flowing speed of the decomposition product entering the reaction chamber are adjusted to ensure that a uniform and continuous amorphous carbon coating layer and a graphitized carbon coating layer are obtained in the reaction process, and simultaneously, the loss of the material is reduced as much as possible.
In some embodiments of the present application, adjusting the VGAnd the value of Mc/M is alternately switched between the first condition and the second condition, and an amorphous carbon coating layer and a graphitized carbon coating layer which are alternately coated are formed on the surface of the silicon substrate material. The amorphous carbon coating layer is a loose amorphous carbon structure, so that the amorphous carbon coating layer plays a buffering role in lithium insertion expansion of a silicon substrate material, and the graphitized carbon coating layerThe layer is a crystal form carbon structure with high graphitization degree, plays a certain constraint role on lithium insertion expansion of the silicon substrate material, and prevents cracking of a coating layer and inactivation of active substances in the lithium extraction process of the silicon substrate material, so that the amorphous carbon structure and the graphitized carbon coating structure which are alternately arranged can better adjust the charge and discharge performance of the silicon substrate negative electrode material, and the cycle life of the battery is prolonged.
In some embodiments of the present application, the molar flow rate M of pyrolysis products is calculated after the atomized carbon source is thermally decomposed in the pre-decomposition zoneCCan be used for measuring CO after oxidation combustion2The content is determined by a method. The gaseous and steam carbon sources directly determine the molar flow rate M of the pyrolysis products according to the molecular structure of the inlet gasC。
In some embodiments of the present application, during the deposition coating reaction, a N-containing substance may be introduced, wherein the N-containing substance includes NH3One or more of acetonitrile, aniline or butylamine.
In the embodiment of the application, the temperature range of the pre-decomposition carbon source substance is set to be 500-1500 ℃, preferably 700-1300 ℃, so that the carbon source substance is changed into a gaseous state in the pre-decomposition area, and a pyrolysis or polycondensation reaction is rapidly carried out to form a pre-decomposition area product capable of rapidly carrying out a subsequent coating reaction. In the pre-decomposition zone, conventional heating means or microwave or radio frequency can be used to reach the desired temperature. However, the microwave heating mode can ionize the substances containing C, and compared with other heating modes, the microwave heating mode can obviously reduce the pre-decomposition temperature and improve the pre-decomposition efficiency.
In some embodiments of the present application, after passing through the pre-decomposition region, the gaseous carbon source material undergoes dehydrogenation, radical addition, and the like to become a linear or aromatic compound with a higher relative molecular mass and a lower gibbs free energy, after passing through the pre-decomposition region, the vaporized carbon source material undergoes dehydrogenation (cracking), radical addition, and the like to become a linear or aromatic compound, and after passing through the pre-decomposition region, the atomized carbon source material undergoes cracking, radical addition, and the like to become a linear or aromatic compound.
In the embodiment of the application, after the pre-decomposition reaction, the mixed gas passing through the pre-decomposition area is a decomposition product, and the decomposition product comprises a non-oxidizing gas introduced into the reaction atmosphere and a pre-decomposed carbon source substance. In some embodiments of the application, the carbon source substance (gaseous state) after pre-decomposition accounts for 1-70% of the volume percentage of the decomposition product, the pre-decomposition reaction step can enable the reaction temperature in the manufacturing method of the silicon-based negative electrode material to be more flexibly controlled, is beneficial to controlling the reaction progress of decomposition, addition and the like of the carbon source substance, and has small interference on the temperature of a coating area.
And then, introducing the decomposition product into a deposition coating area of the coating equipment, so that a silicon substrate material and the carbon source substance subjected to pre-decomposition are subjected to deposition coating reaction, and an amorphous carbon coating layer and a graphitized carbon coating layer are formed on the surface of the silicon substrate material, wherein the amorphous carbon coating layer or the graphitized carbon coating layer is directly coated on the surface of the silicon substrate material.
In some embodiments of the present application, the temperature for the deposition coating reaction is 500 ℃ to 1100 ℃, and preferably, the temperature for the deposition coating reaction is 650 ℃ to 1000 ℃. In the process of generating the deposition coating reaction, if the temperature is too low, the C/H ratio of the coating layer on the surface of the negative electrode material is too high, so that the conductivity is poor, and the performance is influenced. If the temperature is too high, excessive disproportionation of silicon oxide in the silicon substrate material is easily caused, and the capacity and the cycle performance of the silicon-based anode material are affected.
The silicon substrate material comprises one or a mixture of more of metallurgical silicon, silicon oxide SiOx (x is more than or equal to 0 and less than or equal to 1.5) and porous silicon, and the median range of the particle size of the silicon substrate material is 1-20 mu m. In some embodiments of the present application, the silicon substrate material further comprises a compound of the formula MSiOy, wherein (y is more than 0.85 and less than or equal to 3.5, and M is any one or more of Li, Na, Mg, Al, Fe and Ca.
In the process of the deposition coating reaction, N-containing substances can be introduced, wherein the N-containing substances comprise NH3One or more of acetonitrile, aniline or butylamine. And introducing the N-containing substance to obtain an amorphous carbon coating layer and a graphitized carbon coating layer doped with N atoms. The amorphous carbon coating layer and the graphitized carbon coating layer doped with N atoms can further improve the charge-discharge capacity of the silicon-based negative electrode material, and the amorphous carbon coating layer and the graphitized carbon coating layer can further improve the conductivity of the material after nitrogen doping, so that the internal resistance of the battery is reduced, and the large-current charge-discharge capacity of the battery is further ensured.
In some embodiments of the present application, the mass percentage of the amorphous carbon coating layer and the graphitized carbon coating layer in the silicon-based negative electrode material is, for example, 0.01-99: 1, and preferably, the amorphous carbon coating layer accounts for 10-90%, for example, 20%, 30%, 40%, 50%, 60%, 70%, 80%, and the like.
In some embodiments of the present application, the surface of the silicon substrate material in the silicon-based negative electrode material has more than one amorphous carbon coating layer and/or more than one graphitized carbon coating layer, and further, the more than one amorphous carbon coating layers and the more than one graphitized carbon coating layers are alternately arranged.
For example, methane with a flow rate of 10m/min is firstly introduced into the pre-decomposition region, nitrogen is used as a protective gas, the reaction temperature is 1000 ℃, the introduction is stopped after 180 minutes, n-hexane with a flow rate of 1m/min is continuously introduced into the pre-decomposition region, nitrogen is continuously used as a protective gas, and the introduction is stopped after 120 minutes. The process of introducing methane and n-hexane may be carried out alternately.
In another embodiment, propylene with the flow rate of 5m/min is firstly introduced into the pre-decomposition area, Ar is used as protective gas, the reaction is stopped after 300 minutes of introduction at the temperature of 1000 ℃, polypropylene melt with the flow rate of 0.1m/min is continuously introduced into the pre-decomposition area, Ar is used as protective gas continuously, and the reaction is stopped after 240 minutes of introduction. The process of feeding propylene and polypropylene may be carried out alternately.
In another embodiment of the present application, hydrogen is used as the protective gas, and a mixed gas of ethane and ethanol is introduced into the pre-decomposition zone, wherein the flow rate of ethane and ethanol is 50m/min, the reaction temperature is 1200 ℃, and the reaction is stopped after 100 minutes.
Example 1
Using a rotary furnace comprising a predecomposition area and a deposition coating area, selecting 1kg of silicon oxide SiOx (x is 0.9) with the median particle size of 5 μm as a silicon substrate material, using nitrogen as a protective gas, and introducing a flow velocity V into the predecomposition areaG1M/min of a mixture of ethane gas and ethanol vapor, wherein the molar ratio of ethane to ethanol is 1: 1, the reaction temperature is 900 ℃, and M is adjustedcAnd introducing the silicon-based anode material into a deposition coating area of the rotary furnace, wherein the temperature of the deposition coating area is 900 ℃, and the total reaction time is 20min to form the silicon-based anode material S1-1.
The S1-1 material is continuously reacted at the same temperature, and V is introducedGMixed gas of methane and ethylene with the volume ratio of 3: 1 of 10M/min, and M is controlledcand/M is 0.05, the reaction time is 120min, and the silicon-based negative electrode material S1-2 is formed.
The S1-2 material is continuously reacted at the same temperature, and V is introducedGAnd (3) controlling the Mc/M to be 0.5 and the reaction time to be 10min under the condition of 5M/min of benzene vapor, and forming the silicon-based negative electrode material S1-3.
The S1-3 material is continuously reacted at the same temperature, and V is introducedGAnd (3) forming the silicon-based anode material S1-4 by using a mixture of ethane gas and ethanol vapor with the molar ratio of ethane to ethanol being 1: 1, controlling the Mc/M to be 0.25 and reacting for 10 min.
Example 2
Using the same apparatus as in example 1, 1kg of a silicon oxide SiOx (x. about.0.9) having a median particle size of 8 μm was selected as the silicon substrate material, and a flow rate V was passed through the pre-decomposition zone using nitrogen as a protective gasGAnd (2) mixing 10M/min of methane and ethylene, wherein the volume ratio of methane to ethylene is 3: 1, the reaction temperature is 900 ℃, the Mc/M is adjusted to be 0.05mol/min, introducing the mixture into a deposition coating area of the rotary furnace, the temperature of the deposition coating area is 900 ℃, and the total reaction time is 120min, thus forming the silicon-based negative electrode material S2-1.
The S2-1 material is continuously reacted at the same temperature, and V is introducedG1M/min ethane gas and ethanol vapor mixture, wherein the molar ratio of ethane and ethanol is 1: 1, and M is controlledcand/M is 0.25, the reaction time is 10min, and the silicon-based negative electrode material S2-2 is formed.
The S2-2 material is continuously reacted at the same temperature, and V is introducedGMixed gas of methane and ethylene with the volume ratio of 3: 1 of 10M/min, and M is controlledcand/M is 0.05, the reaction time is 120min, and the silicon-based negative electrode material S2-3 is formed.
The S2-3 material is continuously reacted at the same temperature, and V is introducedGControl M for 5M/min benzene vaporcand/M is 0.5, the reaction time is 10min, and the silicon-based negative electrode material S2-4 is formed.
Specific process conditions of examples 3 to 6 refer to table 1.
Comparative example 1
Selecting 1kg of silicon oxide SiOx (x is 0.9) with the median particle size of 5 μ M as a silicon substrate material, using nitrogen as a protective gas, setting the reaction temperature to 900 ℃, and controlling Mcand/M is 0.5, the reaction time is 30min, and the silicon-based negative electrode material D1 is formed.
Comparative example 2
Selecting 1kg of silicon oxide SiOx (x is 0.9) with the median particle size of 5 μ M as a silicon substrate material, setting the reaction temperature to 1000 ℃ with nitrogen as a protective gas, and controlling Mcand/M is 0.05, the reaction time is 300min, and the silicon-based negative electrode material D2 is formed.
Other process conditions for comparative example and comparative example 2 are also referred to in table 1.
Table 1 shows process conditions of the steps of the methods for preparing silicon-based anode materials in examples 1 to 6 and comparative examples 1 and 2, and the detailed process descriptions refer to example 1 and example 2 and the text of comparative examples 1 and 2.
Table 2 shows the respective film thicknesses, the mass percentage contents of carbon elements, and raman spectrum detection data of the amorphous carbon coating layer (AC) and the graphitized carbon coating layer (GC) in the silicon-based anode materials formed by the preparation methods of the silicon-based anode materials in examples 1 to 6, and comparative examples 1 and 2. When the silicon-based negative electrode material is used as a negative electrode material of a lithium battery, the electrochemical performance detection data of the negative electrode material is shown in fig. 2 (the capacity mAh/g, the efficiency% and the 30-week cycle capacity retention rate, wherein the efficiency% refers to the first coulombic efficiency%), the data in the table show that the silicon-based negative electrode material formed by the preparation method of the silicon-based negative electrode material disclosed by the embodiment of the application is far higher than the silicon-based negative electrode material in a comparative test in the capacity mAh/g, the first coulombic efficiency and the 30-week cycle capacity retention rate of the silicon-based negative electrode material in unit mass when the silicon-based negative electrode material is used as the negative electrode material of the lithium battery.
Fig. 1 and fig. 2 in the present application also provide SEM images of the silicon-based negative electrode material according to the embodiment of the present application, and raman spectra of the amorphous carbon coating layer and the graphitized carbon coating layer in the silicon-based negative electrode material according to the embodiment of the present application. As can be seen from fig. 1, the silicon-based negative electrode material particles having the amorphous carbon coating layer and the graphitized carbon coating layer on the surface thereof described in the embodiments of the present application are uniformly dispersed. As can be seen from fig. 2, in the silicon-based negative electrode material, both the amorphous carbon coating layer and the graphitized carbon coating layer have a G peak and a D peak, and the peak intensities of the amorphous carbon coating layer and the graphitized carbon coating layer are different. Wherein line 1 is a graphitized carbon coating and line 2 is an amorphous carbon coating. The Raman spectrum Id/Ig of the amorphous carbon coating layer is 0.92, and the Raman spectrum Id/Ig of the graphitized carbon coating layer is 0.43.
Figure BDA0002358446480000211
Figure BDA0002358446480000221
Table 2 in summary, upon reading the present detailed disclosure, those skilled in the art will appreciate that the foregoing detailed disclosure may be presented by way of example only, and may not be limiting. Those skilled in the art will appreciate that the present application is intended to cover various reasonable variations, adaptations, and modifications of the embodiments described herein, although not explicitly described herein. Such alterations, improvements, and modifications are intended to be suggested by this disclosure, and are within the spirit and scope of the exemplary embodiments of this disclosure.
It is to be understood that the term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
It will be further understood that the terms "comprises," "comprising," "includes" and/or "including," when used herein, specify the presence of stated features, integers, steps, operations, materials, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, materials, components, and/or groups thereof.
Further, exemplary embodiments are described by referring to cross-sectional illustrations and/or plan illustrations that are idealized exemplary illustrations.

Claims (11)

1. A preparation method of a silicon-based anode material comprises the following steps:
in a non-oxidizing atmosphere, making a carbon source substance pass through a pre-decomposition area to form decomposition products, wherein the carbon source substance comprises more than one of a gas carbon source substance, a vaporized carbon source substance or an atomized carbon source substance; and
regulating and controlling the flow velocity V of the decomposition product entering the reaction cavity of the deposition coating areaGAnd the molar flow rate of the decomposition product and the mass ratio Mc/M of the silicon substrate material are used for leading the silicon substrate material and the decomposition product to generate deposition coating reaction in a deposition coating area, forming an amorphous carbon coating layer and a graphitized carbon coating layer on the surface of the silicon substrate material, and directly coating the amorphous carbon coating layer or the graphitized carbon coating layer on the surface of the silicon substrate material, wherein V is more than or equal to 0.01 and less than or equal to VG≤100，0.001≤Mc/M≤1，VGThe unit is M/min, MCThe unit is mol/min, and M is the mass of the silicon substrate material in kg by carbon atoms.
2. The method for preparing a silicon-based anode material according to claim 1, wherein under a first condition: v is more than or equal to 10GWhen Mc/M is less than or equal to 100 and 0.001 and less than 0.1, a graphitized carbon coating layer is formed on the surface of the silicon substrate material; and in a second condition: v is more than or equal to 0.01GWhen Mc/M is more than 0.2 and less than or equal to 1, an amorphous carbon coating layer is formed on the surface of the silicon substrate material.
3. The method of preparing a silicon-based anode material according to claim 2, wherein V is adjustedGAnd the value of Mc/M is alternately switched between a first condition and a second condition, and an amorphous carbon coating layer and a graphitized carbon coating layer which are alternately coated are formed on the surface of the silicon substrate material.
4. The method for preparing the silicon-based anode material as claimed in claim 1, wherein the gaseous carbon source substances comprise methane, ethane, ethylene, acetylene, propane and propylene, the vaporized carbon source substances comprise n-hexane, ethanol and benzene, and the atomized carbon source substances comprise polyethylene and polypropylene.
5. The method for preparing the silicon-based anode material as claimed in claim 1, wherein an N-containing substance is introduced during the deposition coating reaction, wherein the N-containing substance comprises NH3One or more of acetonitrile, aniline or butylamine.
6. The method for preparing a silicon-based anode material according to claim 1,
the non-oxidizing atmosphere refers to a reaction environment including any one or more of hydrogen, nitrogen, or an inert gas.
7. The method for preparing a silicon-based anode material according to claim 1, wherein the temperature range for pre-decomposing the carbon source material is 500 ℃ to 1500 ℃.
8. The method for preparing a silicon-based anode material according to claim 1, wherein the temperature for the deposition coating reaction is 500-1100 ℃.
9. The method for preparing a silicon-based anode material as claimed in claim 7 or 8, wherein the temperature for pre-decomposing the carbon source material is 700 ℃ to 1300 ℃, and the temperature for the deposition coating reaction is 650 ℃ to 1000 ℃.
10. The method for preparing the silicon-based anode material as claimed in claim 1, wherein the silicon substrate material comprises one or more of metallurgical silicon, silicon oxide SiOx with x being 0-1.5, and porous silicon, and the median particle size of the silicon substrate material is in the range of 1 μm-20 μm.
11. The method for preparing a silicon-based anode material as claimed in claim 1, wherein the silicon substrate material further comprises a compound having a general formula of MSiOy, wherein y is more than 0.85 and less than or equal to 3.5; m is any one or more of Li, Na, Mg, Al, Fe and Ca.
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